US20030073756A1 - Radiation curable compositions with enhanced adhesion - Google Patents
Radiation curable compositions with enhanced adhesion Download PDFInfo
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- US20030073756A1 US20030073756A1 US10/243,013 US24301302A US2003073756A1 US 20030073756 A1 US20030073756 A1 US 20030073756A1 US 24301302 A US24301302 A US 24301302A US 2003073756 A1 US2003073756 A1 US 2003073756A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/065—Polyamides; Polyesteramides; Polyimides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31623—Next to polyamide or polyimide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31768—Natural source-type polyamide [e.g., casein, gelatin, etc.]
- Y10T428/31772—Next to cellulosic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31768—Natural source-type polyamide [e.g., casein, gelatin, etc.]
- Y10T428/31772—Next to cellulosic
- Y10T428/31775—Paper
Definitions
- the present invention relates to a radiation-curable composition
- a radiation-curable composition comprising the reaction product of an amine-terminated (poly)aminoamide and a mono-(meth)acrylate or a poly-(meth)acrylate.
- the compositions according to the invention are liquids at room temperature.
- the invention also pertains to a method of producing a coated substrate comprising contacting a substrate with the composition according to the invention and subjecting the composition to high energy electrons or ultraviolet light.
- the compositions according to the invention can also be cured via thermal polymerization using well known free radical initiators such as organic peroxides.
- Radiation cured compositions according to the invention deposited on a substrate exhibit excellent adhesion characteristics to the substrate.
- (meth)acrylate means a mono-acrylate or a methacrylate ester.
- poly-(meth)acrylate means a compound having two or more acrylate or methacrylate ester groups.
- (poly)aminoamide includes a mono-aminoamide or a polyaminoamide.
- the amine-terminated (poly)aminoamide s according to the invention can be made by the reaction between a di- or poly basic carboxylic acids and excess polyfunctional amines to produce amine-terminated (poly)aminoamides.
- the acids can be saturated, unsaturated fatty acids or a combination thereof and/or its dimers of unsaturated fatty acids such as a C 36 dimer acid.
- the polyfunctional amines can be linear polyalkylene polyamine examples of which include, but are not limited to, ethylene diamine, 1,6-hexamethylene diamine, trimethylpentanediamine, diethylene triamine, triethylene tetramine, tetraethylene teraamine; cyclic polyamines such as piperazine, isophorone diamine, meta-xylene diamine, norbornane diamine, 1,3-diaminomethyl cyclohexane and polyether based polyamines available commercially as JEFFAMINE® D-230, T-403 and D-2000.
- the (meth)acrylates according to the invention can be any di- or polyfunctional (meth)acrylates. Such compounds include compounds having both acrylate and methacrylate groups.
- Examples of the (meth)acrylates according to the invention include, but are not limited to, (a) the reaction product of the diglycidyl ethers of aliphatic diols and (meth)acrylate acid such as butanedioldiglycidyl ether and (meth)acrylate acid, the mono-glycidyl ether of (meth)acrylate acid and (meth)acrylate acid; a mixed acrylate-methacrylate ester of butanedioldiglycidyl ether; (b) (meth)acrylate-terminated urethanes made by the reaction of a diisocyanate and 2-hydroxyethyl (meth)acrylate, of a diisocyanate and the reaction product of succinic anhydride and (meth)acrylate acid.
- the ratio of (meth)acrylate to amine-terminated (poly)aminoamide can vary from about 100 to about 1 (meth)acrylate equivalence to amine hydrogen equivalence, preferably from about 15 to about 1 and most preferably about 8 to about 1 ratio in terms of (meth)acrylate to amine hydrogen equivalence.
- compositions according to the invention can optionally contain acid functional (meth)acrylates.
- the acid functional (meth)acrylate according to the invention can be made by the reaction between dicarboxylic acid anhydrides and hydroxyalkyl (meth)acrylates.
- anhydrides that can be used include, but are not limited to, succinic anhydride, maleic anhydride, alkenyl succinic anhydrides such as dodecenyl succinic anhydride and octenyl succinic anhydride, trimellitic and phthalic anhydrides.
- hydroxyalkyl (meth)acrylates includes hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and methacrylate, hydroxybutyl acrylate and methacrylate and caprolactone or polycaprolactone esterified with above hydroxyalkyl acrylate and methacrylates.
- compositions according to the invention can optionally contain photoinitiators such as benzophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, ⁇ , ⁇ -diethoxyacetophenone and alkyl benzoin ethers.
- photoinitiators such as benzophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, ⁇ , ⁇ -diethoxyacetophenone and alkyl benzoin ethers.
- compositions according to the invention can be applied to any type of substrate such as, for example, non porous substrates, such as glass, plastics and metals, and porous substrates, such as wood, paper and leather by any means known to those skilled in the art such as by spraying, dipping, brushing, etc.
- the compositions according to the invention can be cured by any type of radiation that is typically used such as high energy electrons (electron beams) and ultraviolet light.
- the compositions according to the invention can also be cured thermally in the presence of a free radical initiator such as benzoyl peroxide or azo-bisisobutyronitrile.
- the above mixture is combined with 5 parts of trimethylolpropane triacrylate, 1 part of ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone and 5 parts of benzophenone to give a uniform composition with a viscosity of 160 cps.
- a 3 mil draw down of the above composition was applied over steel substrate and cured with UV light having energy of 0.668 joules/cm 2 .
- the UV cured film was hard and slippery with excellent adhesion to the substrate.
- Dimerized fatty acid and piperazine are added in a reaction kettle and heated to 227° C. for one hour and a vacuum of 15 mm Hg is applied for three hours to remove the water of reaction.
- a reaction carried out in this manner should produce a polyamide resin having an amine value of about 67 mg KOH/gm.
- Butanediol diglycidylether, triphenylphosphine and hydroquinone monomethyl ether is charged in a resin kettle and heated to 45° C. Acrylic acid is added over time by maintaining the reaction temperature below 80° C. The above reaction mixture is kept at 80-90° C. until the acid value is below 5 and all of the epoxide is reacted. The resulting diacrylate is cooled to 45° C. and added with charge 2. Once the exotherm is subsided, the reaction mixture is heated to 80° C. and kept at this temperature until all of the polyamide is reacted. A reaction carried out in this manner should produce a polyamide-acrylate resin that is a liquid at room temperature.
- Polyamide resin, triphenylphosphine and hydroquinone monomethylether are added in a reaction kettle and heated to 60° C.
- GMA is added to the kettle over time by keeping the temperature below 80° C.
- Reaction mixture is kept at 80° C. until all of the epoxide group from GMA is reacted.
- the resulting polyamide-methacrylate resin solution is cooled to 60° C. and poured out. A reaction carried out in this manner should produce a polyamide-methacrylate resin that is a liquid at room temperature.
- Charge 1 is reacted using conditions as in example 5 to produce mono methacrylate of butanedioldiglycidylether.
- the monomethacrylate is reacted with the Polyamide.
- a reaction carried out in this manner should produce a polyamide-methacrylate resin that is a liquid at room temperature.
- Urethane diacrylate is made by heating the charge 1 in a reaction kettle to 80° C. and holding the reaction mixture at that temp. until all of the isocyanates are reacted. The resulting product, urethane diacrylate is cooled to 60° C. and added and reacted with Polyamide. A reaction carried out in this manner should produce a polyamide-acrylate resin that is a liquid at room temperature.
- a polyamide resin is prepared in a resin kettle from a mixture of 81.09% by weight EMPOL® 1025 Dimer Acid (hydrogenated dimerized fatty acid mixture available from Cognis Corporation), and 18.91% by weight piperazine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was a viscous liquid with an Mn value of 1570 and a Mw value of 3660. The product titrated with HCl to bromocresol green end-point to show an amine value of 67 mg KOH/gram
- a polyamide resin is prepared in a resin kettle from a mixture of 78.65% by weight EMPOL® 1025 Dimer Acid (hydrogenated dimerized fatty acid mixture available from Cognis Corporation), 12.18% 1,2-cyclohexanediamine, and 9.17% by weight piperazine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was a viscous liquid. The product titrated with HCI to bromocresol green end-point to show an amine value of 56 mg KOH/gram.
- a polyamide resin is prepared in a resin kettle from a mixture of 82.88% by weight EMPOL® 1061 (distilled dimerized fatty acid mixture available from Cognis Corporation), 5.46% ethylenediamine, and 11.66% by weight piperazine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was a slightly tacky solid. The product titrated with HCl to bromocresol green end-point to show an amine value of 49.2 mg KOH/gram. The amid-amine resin had an Mn of 1930 and an Mw of 4030 by GPC. A solution was prepared containing 50% resin solids, 1% water, and 49% 2-propanol.
- a polyamide resin is prepared in a resin kettle from a mixture of 76.02% by weight EMPOL® 1061 Dimer Acid (distilled dimerized fatty acid mixture available from Cognis Corporation), 7.62% ethylenediamine, and 16.36% by weight aminoethyl-piperazine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was a slightly tacky solid. The product titrated with HCI to bromocresol green end-point to show an amine value of 112 mg KOH/gram.
- the amido-amine resin had an Mn of 1410 and an Mw of 2000 by GPC.
- a solution was prepared containing 64.3% resin solids and 35.7% 2-propanol.
- a polyamide resin is prepared in a resin kettle from a mixture of 63.88% by weight EMPOL® 1061 (distilled dimerized fatty acid mixture available from Cognis Corporation) and 36.12% by weight isophorone diamine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was an amber solid. The product titrated with HCl to bromocresol green end-point to show an amine value of 79.2 mg KOH/gram.
- the amido-amine resin had an Mn of 1770 and an Mw of 2680 by GPC.
- a solution was prepared containing 74% resin.
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- Macromonomer-Based Addition Polymer (AREA)
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Abstract
Description
- This application claims the benefit of copending provisional application serial No. 60/326,978, filed on Oct. 4, 2001, the entire contents of which are incorporated herein by reference.
- Use of Ultra-Violet/Electron Beam curable compositions in the coatings and inks industries has been growing tremendously in the last few years due to their ability to cure instantaneously with optimal film properties such as chemical, stain and abrasion resistance. Since vinyl polymerization occurs with substantial volume contraction, adhesion of radiation curable compositions to non porous substrates, such as glass, plastics and metals, and porous substrates, such as wood, paper and leather, remains a challenging problem to formulators.
- The present invention relates to a radiation-curable composition comprising the reaction product of an amine-terminated (poly)aminoamide and a mono-(meth)acrylate or a poly-(meth)acrylate. The compositions according to the invention are liquids at room temperature. The invention also pertains to a method of producing a coated substrate comprising contacting a substrate with the composition according to the invention and subjecting the composition to high energy electrons or ultraviolet light. The compositions according to the invention can also be cured via thermal polymerization using well known free radical initiators such as organic peroxides.
- Radiation cured compositions according to the invention deposited on a substrate exhibit excellent adhesion characteristics to the substrate.
- The term (meth)acrylate means a mono-acrylate or a methacrylate ester. The term poly-(meth)acrylate means a compound having two or more acrylate or methacrylate ester groups. The term (poly)aminoamide includes a mono-aminoamide or a polyaminoamide.
- The amine-terminated (poly)aminoamide s according to the invention can be made by the reaction between a di- or poly basic carboxylic acids and excess polyfunctional amines to produce amine-terminated (poly)aminoamides. The acids can be saturated, unsaturated fatty acids or a combination thereof and/or its dimers of unsaturated fatty acids such as a C36 dimer acid. The polyfunctional amines can be linear polyalkylene polyamine examples of which include, but are not limited to, ethylene diamine, 1,6-hexamethylene diamine, trimethylpentanediamine, diethylene triamine, triethylene tetramine, tetraethylene teraamine; cyclic polyamines such as piperazine, isophorone diamine, meta-xylene diamine, norbornane diamine, 1,3-diaminomethyl cyclohexane and polyether based polyamines available commercially as JEFFAMINE® D-230, T-403 and D-2000.
- The (meth)acrylates according to the invention can be any di- or polyfunctional (meth)acrylates. Such compounds include compounds having both acrylate and methacrylate groups. Examples of the (meth)acrylates according to the invention include, but are not limited to, (a) the reaction product of the diglycidyl ethers of aliphatic diols and (meth)acrylate acid such as butanedioldiglycidyl ether and (meth)acrylate acid, the mono-glycidyl ether of (meth)acrylate acid and (meth)acrylate acid; a mixed acrylate-methacrylate ester of butanedioldiglycidyl ether; (b) (meth)acrylate-terminated urethanes made by the reaction of a diisocyanate and 2-hydroxyethyl (meth)acrylate, of a diisocyanate and the reaction product of succinic anhydride and (meth)acrylate acid.
- The ratio of (meth)acrylate to amine-terminated (poly)aminoamide can vary from about 100 to about 1 (meth)acrylate equivalence to amine hydrogen equivalence, preferably from about 15 to about 1 and most preferably about 8 to about 1 ratio in terms of (meth)acrylate to amine hydrogen equivalence.
- The compositions according to the invention can optionally contain acid functional (meth)acrylates. The acid functional (meth)acrylate according to the invention can be made by the reaction between dicarboxylic acid anhydrides and hydroxyalkyl (meth)acrylates. Examples of anhydrides that can be used include, but are not limited to, succinic anhydride, maleic anhydride, alkenyl succinic anhydrides such as dodecenyl succinic anhydride and octenyl succinic anhydride, trimellitic and phthalic anhydrides. Examples of hydroxyalkyl (meth)acrylates includes hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and methacrylate, hydroxybutyl acrylate and methacrylate and caprolactone or polycaprolactone esterified with above hydroxyalkyl acrylate and methacrylates.
- The compositions according to the invention can optionally contain photoinitiators such as benzophenone, α, α-dimethoxy-α-phenylacetophenone, α, α-diethoxyacetophenone and alkyl benzoin ethers.
- The compositions according to the invention can be applied to any type of substrate such as, for example, non porous substrates, such as glass, plastics and metals, and porous substrates, such as wood, paper and leather by any means known to those skilled in the art such as by spraying, dipping, brushing, etc. The compositions according to the invention can be cured by any type of radiation that is typically used such as high energy electrons (electron beams) and ultraviolet light. The compositions according to the invention can also be cured thermally in the presence of a free radical initiator such as benzoyl peroxide or azo-bisisobutyronitrile.
- In a clean container weigh 61.0 parts (0.4066 equiv.) of tripropylene glycol diacrylate with an acrylate equivalent weight of 150 and add 7 parts (0.0722 equiv.) of VERSAMID® 140 (polyaminoamide based on Tallow oil fatty acid and its dimer polymer with triethylene tetramine) with an amine hydrogen equivalent of 97, with stirring. The resulting product mixture is added with 14 parts of mono[2-[(1-oxo-2-propenyl)oxy]ethyl]ester of butanedioic acid (made by addition reaction of one mole of succinic anhydride with one mole of hydroxyethylacrylate) and mixed thoroughly. The above mixture is combined with 5 parts of trimethylolpropane triacrylate, 1 part of α, α-dimethoxy-α-phenylacetophenone and 5 parts of benzophenone to give a uniform composition with a viscosity of 160 cps. A 3 mil draw down of the above composition was applied over steel substrate and cured with UV light having energy of 0.668 joules/cm2. The UV cured film was hard and slippery with excellent adhesion to the substrate.
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Preparation of Liquid Polyaminoamide Charge: Dimerized fatty acid (EMPOL ® 10251) 580.6 gm(2.0 eq.) Piperazine 135.4 gm(3.2 eq.). - Dimerized fatty acid and piperazine are added in a reaction kettle and heated to 227° C. for one hour and a vacuum of 15 mm Hg is applied for three hours to remove the water of reaction. A reaction carried out in this manner should produce a polyamide resin having an amine value of about 67 mg KOH/gm.
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Reaction of Polyamide with diacrylate of butanedioldiglycidylether Charge 1. Butanediololdiglycidylether 20.2 gm(0.2 eq.) Acrylic acid 14.4 gm(0.2 eq.) Triphenylphosphine 0.1 gm Hydroquinone monomethylether 0.1 gm 2. Polyamide from Example 1 83.7 gm(0.1 eq.) - Butanediol diglycidylether, triphenylphosphine and hydroquinone monomethyl ether is charged in a resin kettle and heated to 45° C. Acrylic acid is added over time by maintaining the reaction temperature below 80° C. The above reaction mixture is kept at 80-90° C. until the acid value is below 5 and all of the epoxide is reacted. The resulting diacrylate is cooled to 45° C. and added with charge 2. Once the exotherm is subsided, the reaction mixture is heated to 80° C. and kept at this temperature until all of the polyamide is reacted. A reaction carried out in this manner should produce a polyamide-acrylate resin that is a liquid at room temperature.
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Reaction of Polyamide with acrylic acid-methacrylic acid adduct of butanedioldiglycidylether Charge 1. Butanedioldiglycidylether 20.2 gm(0.2 eq.) Acrylic acid 7.2 gm(0.1 eq.) Methacrylic acid 8.4 gm(0.1 eq.) Triphenylphosphine 0.1 gm Hydroquinone monomethylether 0.1 gm 2. Polyamide from Example 1 83.7 gm(0.1 eq.) - Charge 1 is added to the reaction kettle and reacted to produce the adducts of butanedioldiglycidylether containing both acrylate and methacrylate functionalities using conditions described in example 3. The above adduct is reacted with the Polyamide. A reaction carried out in this manner should produce a polyamide-methacrylate resin that is a liquid at room temperature.
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Reaction of Polyamide with GMA-Acrylic acid adduct Charge: 1. Glycidylmethacrylate 14.2 gm(0.1 eq.) Triphenyl phosphine 0.1 gm Hydroquinone monomethylether 0.1 gm 2. Acrylic acid 7.2 gm(0.1 eq.) 3. Polyamide from Example 1 83.7 gm(0.1 eq.) - Charge 1 is added to a reaction kettle and heated to 40-45° C. Charge 2 is added over time by keeping the reaction temperature below 80° C. due to exotherm. Reaction is continued at 80-90° C. until all of GMA is reacted. The resulting GMA-acrylic acid adduct is cooled to 40-50° C. and added with charge 3 over time by keeping the reaction mixture below 80° C. After the addition of charge 3, the reaction mixture is kept at 80-90° C. to complete the amine-acrylate addition reaction. A reaction carried out in this manner should produce a polyamide-acrylate resin that is a liquid at room temperature.
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Reaction of Polyamide with glycidyl methacrylate Charge: Glycidyl methacrye(GMA)1 14.2 gm(0.1 eq.) Polyamide from Example 1 83.7 gm(0.1 eq.) Triphenylphosphine 0.1 gm Hydroquinone monomethylether 0.1 gm - Polyamide resin, triphenylphosphine and hydroquinone monomethylether are added in a reaction kettle and heated to 60° C. GMA is added to the kettle over time by keeping the temperature below 80° C. Reaction mixture is kept at 80° C. until all of the epoxide group from GMA is reacted. The resulting polyamide-methacrylate resin solution is cooled to 60° C. and poured out. A reaction carried out in this manner should produce a polyamide-methacrylate resin that is a liquid at room temperature.
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Reaction of Polyamide with monomethacrylate of butanedioldiglycidylether Charge 1. Butanedioldiglycidylether 20.2(0.2 eq.) Methacrylic acid 8.4(0.1 eq.) Triphenylphosphine 0.1 gm Hydroquinone monomethylether 0.1 gm 2. Polyamide from Example 1 83.7 gm(0.1 eq.) - Charge 1 is reacted using conditions as in example 5 to produce mono methacrylate of butanedioldiglycidylether. The monomethacrylate is reacted with the Polyamide. A reaction carried out in this manner should produce a polyamide-methacrylate resin that is a liquid at room temperature.
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Reaction of Polyamide with urethane diacrylate Charge 1. Isophorone diisocyanate1 22.2. gm(0.2 eq.) Tone M-1002 (hydroxy functional acrylate) 68.8 gm(0.2 eq) Dibutytindilaurate 0.1 gm Hydroquinone monomethylether 0.1 gm 2. Polyamide from Example 1 83.7 gm(0.1 eq.) - Urethane diacrylate is made by heating the charge 1 in a reaction kettle to 80° C. and holding the reaction mixture at that temp. until all of the isocyanates are reacted. The resulting product, urethane diacrylate is cooled to 60° C. and added and reacted with Polyamide. A reaction carried out in this manner should produce a polyamide-acrylate resin that is a liquid at room temperature.
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Reaction of polyamide with isocyanate functional methacrylate monomer Charge 1. Isophorone diisocyanate 22.2 gm(0.2eq) Hydroxyethyl methacrylate 13.0(0.1 eq.) Dibutyltindilaurate 0.1 gm Hydroquinone monomethylether 0.1 gm 2. Polyamide from Example 1 83.7 gm(0.1 eq.) - First half of the isocyanate in Isophorone diisocyanate is reacted with hydroxyethyl methacrylate using conditions described in Example 8. The resulting isocyanate functional urethane methacrylate is reacted with Polyamide to produce polyamide-methacrylate resin.
- A polyamide resin is prepared in a resin kettle from a mixture of 81.09% by weight EMPOL® 1025 Dimer Acid (hydrogenated dimerized fatty acid mixture available from Cognis Corporation), and 18.91% by weight piperazine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was a viscous liquid with an Mn value of 1570 and a Mw value of 3660. The product titrated with HCl to bromocresol green end-point to show an amine value of 67 mg KOH/gram
- A polyamide resin is prepared in a resin kettle from a mixture of 78.65% by weight EMPOL® 1025 Dimer Acid (hydrogenated dimerized fatty acid mixture available from Cognis Corporation), 12.18% 1,2-cyclohexanediamine, and 9.17% by weight piperazine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was a viscous liquid. The product titrated with HCI to bromocresol green end-point to show an amine value of 56 mg KOH/gram.
- A polyamide resin is prepared in a resin kettle from a mixture of 82.88% by weight EMPOL® 1061 (distilled dimerized fatty acid mixture available from Cognis Corporation), 5.46% ethylenediamine, and 11.66% by weight piperazine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was a slightly tacky solid. The product titrated with HCl to bromocresol green end-point to show an amine value of 49.2 mg KOH/gram. The amid-amine resin had an Mn of 1930 and an Mw of 4030 by GPC. A solution was prepared containing 50% resin solids, 1% water, and 49% 2-propanol.
- A polyamide resin is prepared in a resin kettle from a mixture of 76.02% by weight EMPOL® 1061 Dimer Acid (distilled dimerized fatty acid mixture available from Cognis Corporation), 7.62% ethylenediamine, and 16.36% by weight aminoethyl-piperazine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was a slightly tacky solid. The product titrated with HCI to bromocresol green end-point to show an amine value of 112 mg KOH/gram. The amido-amine resin had an Mn of 1410 and an Mw of 2000 by GPC. A solution was prepared containing 64.3% resin solids and 35.7% 2-propanol.
- A polyamide resin is prepared in a resin kettle from a mixture of 63.88% by weight EMPOL® 1061 (distilled dimerized fatty acid mixture available from Cognis Corporation) and 36.12% by weight isophorone diamine. The mixture was refluxed for one hour before heating to 227° C. (440° F.) while collecting distillate. Material was held at 227° C. for one hour under nitrogen flow and then three hours at the same temperature under a vacuum of 15 mm Hg. The resulting product was an amber solid. The product titrated with HCl to bromocresol green end-point to show an amine value of 79.2 mg KOH/gram. The amido-amine resin had an Mn of 1770 and an Mw of 2680 by GPC. A solution was prepared containing 74% resin.
- 81.6 grams of resin/2-propanol solution from example 14 was mixed with 7.99 grams maleic anhydride and 12.75 grams toluene. The product titrated with HCI to bromocresol green end-point to show an amine value of <0.2 mg KOH/gram. The resin solution was titrated with ethanolic KOH to a phenophthalein end-point to show an acid value of 68.2 mg KOH/gram based on resin solids. The resulting maleic amide-acid terminated resin had an Mn of 1700 and an Mw of 2770 by GPC.
- 81.6 grams of resin/2-propanol solution from example 14 was mixed with 7.99 grams maleic anhydride and 12.75 grams toluene. The product titrated with HCl to bromocresol green end-point to show an amine value of <0.2 mg KOH/gram. The resin solution was titrated with ethanolic KOH to a phenophthalein end-point to show an acid value of 68.2 mg KOH/gram. The resulting maleic amide-acid terminated resin had an Mn of 1700 and an Mw of 2770 by GPC.
- 92.74 grams of viscous liquid resin from Example 11 was dissolved in 30 grams toluene and then mixed with 9.05 grams maleic anhydride.
- 73.92 grams of resin/2-propanol solution from Example 13 was mixed with 16.35 grams glycidyl methacrylate (from Dow Chemical Co). The resin solution was heated to 50° C. for 5 hours.
- 99.84 grams of resin/2-propanol solution from Example 14 was mixed with 18.25 grams glycidyl methacrylate (from Dow Chemical Co). The resin solution was heated to 50° C. for 5 hours.
- 81.79 grams of resin/2-propanol solution from Example 12 was mixed with 5.10 grams glycidyl methacrylate (from Dow Chemical Co). The resin solution was heated to 50° C. for 5 hours.
- 106.56 grams of viscous liquid resin from Example 11 was dissolved in 30.50 grams toluene and then mixed with 15.10 grams glycidyl methacrylate (from Dow Chemical Co). The resin solution was heated to 50° C. for 5 hours.
Claims (12)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/243,013 US6809127B2 (en) | 2001-10-04 | 2002-09-13 | Radiation curable compositions with enhanced adhesion |
DE60228745T DE60228745D1 (en) | 2001-10-04 | 2002-10-02 | BY IRRADIATION HARDENABLE COMPOSITIONS WITH IMPROVED ADHESION |
AT02776100T ATE407002T1 (en) | 2001-10-04 | 2002-10-02 | RADIATION-CURABLE COMPOSITIONS WITH IMPROVED ADHESION |
EP02776100A EP1439951B1 (en) | 2001-10-04 | 2002-10-02 | Radiation curable compositions with enhanced adhesion |
PCT/US2002/031532 WO2003028992A1 (en) | 2001-10-04 | 2002-10-02 | Radiation curable compositions with enhanced adhesion |
ES02776100T ES2312628T3 (en) | 2001-10-04 | 2002-10-02 | CURABLE COMPOSITIONS BY RADIATION WITH IMPROVED ADHESION. |
TW91122820A TWI273119B (en) | 2001-10-04 | 2002-10-03 | Radiation curable compositions with enhanced adhesion |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US32697801P | 2001-10-04 | 2001-10-04 | |
US10/243,013 US6809127B2 (en) | 2001-10-04 | 2002-09-13 | Radiation curable compositions with enhanced adhesion |
Publications (2)
Publication Number | Publication Date |
---|---|
US20030073756A1 true US20030073756A1 (en) | 2003-04-17 |
US6809127B2 US6809127B2 (en) | 2004-10-26 |
Family
ID=26935514
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/243,013 Expired - Lifetime US6809127B2 (en) | 2001-10-04 | 2002-09-13 | Radiation curable compositions with enhanced adhesion |
Country Status (7)
Country | Link |
---|---|
US (1) | US6809127B2 (en) |
EP (1) | EP1439951B1 (en) |
AT (1) | ATE407002T1 (en) |
DE (1) | DE60228745D1 (en) |
ES (1) | ES2312628T3 (en) |
TW (1) | TWI273119B (en) |
WO (1) | WO2003028992A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040152239A1 (en) * | 2003-01-21 | 2004-08-05 | Taiwan Semiconductor Manufacturing Co., Ltd. | Interface improvement by electron beam process |
WO2006067639A2 (en) * | 2004-12-10 | 2006-06-29 | Sun Chemical Limited | Acrylated polyamides,their preparation and uses |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7871685B2 (en) * | 2004-04-08 | 2011-01-18 | Tdk Corporation | Methods for producing optical recording medium and optical recording medium |
US9623631B2 (en) * | 2005-06-22 | 2017-04-18 | Henkel IP & Holding GmbH | Radiation-curable laminating adhesives |
GB2429977A (en) * | 2005-09-07 | 2007-03-14 | Sun Chemical Ltd | Acrylated polyamide containing printing inks |
US20070269658A1 (en) * | 2006-05-05 | 2007-11-22 | Kondos Constantine A | Solvent-borne coating compositions, related methods and substrates |
WO2009049781A2 (en) * | 2007-10-15 | 2009-04-23 | Cognis Ip Management Gmbh | Acrylated polyaminoamides (ii) |
US11972948B2 (en) | 2018-06-13 | 2024-04-30 | Brewer Science, Inc. | Adhesion layers for EUV lithography |
FR3111902B1 (en) | 2020-06-30 | 2023-03-10 | Arkema France | (METH)ACRYLATE FUNCTIONALIZED AMIDE-CONTAINING OLIGOMERS |
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US4141867A (en) * | 1976-08-17 | 1979-02-27 | Deutsche Texaco Aktiengesellschaft | Cold cross-linking dispersion adhesive |
US5019608A (en) * | 1987-07-30 | 1991-05-28 | Lord Corporation | Rubber-modified epoxy adhesive compositions |
US5180792A (en) * | 1990-02-21 | 1993-01-19 | Koei Chemical Co., Ltd. | Amine-cured epoxy resin with phenoxyethyl (meth) acrylates |
Family Cites Families (7)
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US4975498A (en) * | 1988-12-14 | 1990-12-04 | Union Camp Corporation | Thermally-curable aminoamide acrylate polymer |
US4987160A (en) | 1989-01-31 | 1991-01-22 | Union Camp Corporation | Radiation-curable aminoamide acrylate polymer |
DE4130834A1 (en) | 1991-09-17 | 1993-03-18 | Roehm Gmbh | PLASTISOL SYSTEMS WITH IMPROVED LIABILITY |
DE4134081A1 (en) | 1991-10-15 | 1993-04-22 | Schering Ag | METHOD FOR PRODUCING LATENT HARDENERS FOR EPOXY RESINS AND THE USE THEREOF |
IT1277088B1 (en) * | 1995-12-14 | 1997-11-04 | Roofing Italiana S R L | PROCEDURE FOR THE RAPID REMOVING OF PLASTIC PRODUCTS OBTAINED BY MOLDING |
US5889076A (en) | 1996-04-08 | 1999-03-30 | Henkel Corporation | Radiation curable rheology modifiers |
US5804671A (en) | 1996-04-08 | 1998-09-08 | Henkel Corporation | Radiation curable rheology modifiers |
-
2002
- 2002-09-13 US US10/243,013 patent/US6809127B2/en not_active Expired - Lifetime
- 2002-10-02 EP EP02776100A patent/EP1439951B1/en not_active Expired - Lifetime
- 2002-10-02 DE DE60228745T patent/DE60228745D1/en not_active Expired - Lifetime
- 2002-10-02 AT AT02776100T patent/ATE407002T1/en not_active IP Right Cessation
- 2002-10-02 ES ES02776100T patent/ES2312628T3/en not_active Expired - Lifetime
- 2002-10-02 WO PCT/US2002/031532 patent/WO2003028992A1/en not_active Application Discontinuation
- 2002-10-03 TW TW91122820A patent/TWI273119B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4141867A (en) * | 1976-08-17 | 1979-02-27 | Deutsche Texaco Aktiengesellschaft | Cold cross-linking dispersion adhesive |
US5019608A (en) * | 1987-07-30 | 1991-05-28 | Lord Corporation | Rubber-modified epoxy adhesive compositions |
US5180792A (en) * | 1990-02-21 | 1993-01-19 | Koei Chemical Co., Ltd. | Amine-cured epoxy resin with phenoxyethyl (meth) acrylates |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040152239A1 (en) * | 2003-01-21 | 2004-08-05 | Taiwan Semiconductor Manufacturing Co., Ltd. | Interface improvement by electron beam process |
WO2006067639A2 (en) * | 2004-12-10 | 2006-06-29 | Sun Chemical Limited | Acrylated polyamides,their preparation and uses |
WO2006067639A3 (en) * | 2004-12-10 | 2006-08-24 | Sun Chemical Ltd | Acrylated polyamides,their preparation and uses |
US20090306242A1 (en) * | 2004-12-10 | 2009-12-10 | Derek Ronald Illsley | Acrylated polyamides |
US8476334B2 (en) * | 2004-12-10 | 2013-07-02 | Sun Chemical Corporation | Acrylated polyamides |
Also Published As
Publication number | Publication date |
---|---|
EP1439951A1 (en) | 2004-07-28 |
US6809127B2 (en) | 2004-10-26 |
EP1439951A4 (en) | 2005-07-27 |
WO2003028992A1 (en) | 2003-04-10 |
EP1439951B1 (en) | 2008-09-03 |
ES2312628T3 (en) | 2009-03-01 |
ATE407002T1 (en) | 2008-09-15 |
TWI273119B (en) | 2007-02-11 |
DE60228745D1 (en) | 2008-10-16 |
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